Multidimensional Gas Chromatography System Research Articles

A two-run heart-cut multidimensional gas chromatography method using flame ionization and mass spectrometry for automated and robust determination of nearly complete wine aroma-volatile profiles

A quantitative analytical method capable of determining the concentrations of 81 aroma-relevant wine volatiles covering nine orders of magnitude was developed and validated in this study. The method is based on stir bar sorptive extraction (SBSE) of 200 μL of wine diluted with 1.8 mL NaCl brine with pH 3.5. Volatiles thermally desorbed from the stir bars were separated in two runs in a heart-cut multidimensional gas chromatographic system and quantified using either a flame ionization detector (FID) in the first dimension (27 aroma compounds) or a mass spectrometer in the second dimension (54 aroma compounds, transferred to 22 cuts). Typical limits of compound detection lay around 0.02 mg/L by FID or ranged from 0.001 to 0.30 μg/L by mass spectrometry detector, liying below the corresponding odor thresholds in all cases. Linearity, reproducibility, and recovery were considered satisfactory for most compounds, with typical R2 values of 0.989–0.999, relative standard deviation below 10 % for 37 compounds and between 10 and 20 % for 44 compounds, and recovery rates of approximately 100 % (85–109 %) for all but acetaldehyde. An analysis of 20 wine samples completed our validation of the method, showing that a single-sample preparation procedure combined with heart-cut multidimensional two-detector gas chromatography can determine wine volatile concentrations ranging from 350 mg/L of isoamyl alcohol to 3.8 ng/L of 3-isobutyl-2-methoxypyrazine.

Optimization of an online heart-cutting multidimensional gas chromatography clean-up step for isotopic ratio mass spectrometry and simultaneous quadrupole mass spectrometry measurements of endogenous anabolic steroid in urine.

Measuring carbon isotope ratios (CIRs) of urinary analytes represents a cornerstone of doping control analysis and has been particularly optimized for the detection of the misuse of endogenous steroids. Isotope ratio mass spectrometry (IRMS) of appropriate quality, however, necessitates adequate purities of the investigated steroids, which requires extensive pre-analytical sample clean-up steps due to both the natural presence of the target analytes and the high complexity of the matrix. In order to accelerate the sample preparation and increase the automation of the process, the use of multidimensional gas chromatography (MDGC) prior to IRMS experiments, was investigated. A well-established instrumental configuration based on two independent GC ovens and one heart-cutting device was optimized. The first dimension (1D) separation was obtained by a non-polar column which assured high efficiency and good loading capacity, while the second dimension (2D), based on a mid-polar stationary phase, provided good selectivity. A flame ionization detector monitored the 1D, and the 2D was simultaneously recorded by isotope ratio and quadrupole mass spectrometry. The assembled MDGC set-up was applied for measuring testosterone, 5α- and 5β-androstanediol, androsterone, and etiocholanolone as target compounds and pregnanediol as endogenous reference compound. The urine sample were pretreated by conventional sample preparation steps comprising solid-phase extraction, hydrolysis, and liquid-liquid extraction. The extract obtained was acetylated and different aliquots were injected into the MDGC system. Two high performance liquid chromatography steps, conventionally adopted prior to CIR measurements, were replaced by the MDGC approach. The obtained values were consistent with the conventional ones. Copyright © 2016 John Wiley & Sons, Ltd.

Determination of nitroalkanes in mainstream cigarette smoke by heart-cutting multidimensional gas chromatography system coupled with mass spectrometry detection

In this paper, heart-cutting two-dimensional GC/MS (GC–GC/MS) method in combination with a simple sample collection procedure was developed for the determination of 6 nitroalkanes in mainstream cigarette smoke. The method could remove large amounts of impurities on-line in the first polar column by heart-cuts and separate from the left interferences in a second mid-polar column. And the target compounds could be focused at the inlet of the second column by cryo-concentration. Compared to conventional GC/MS, GC–GC/MS achieved a lower noise level and sensitivity at least an order of magnitude higher. Furthermore, the GC–GC/MS method could avoid the false negative and false positive results that appeared in the compared conventional GC/MS analysis. By trapping the vapor phase of 20 cigarettes smoke, the LODs and LOQs of the nitroalkanes were 1.3 to 9.8 and 4.3 to 32.6ng/cigarette, respectively, and all linear correlation efficiencies were larger than 0.999. The validation results also indicate that the method has high accuracy (spiked recoveries between 84% and 102%) and good repeatability (RSD between 7.2% and 9.4%). The developed method was applied to analyze 1 Kentucky reference cigarette (3R4F) and 10 Chinese commercial brands of cigarettes. The research results indicated that nitromethane, nitroethane, 2-nitropropane and 1-nitro-n-pentane were detected in mainstream cigarette smoke, but 1-nitro-n-butane and 2-nitropropane, which were reported by one previous study, were not detected in all cigarette samples.

Analysis of irradiated cooked ham by direct introduction into the programmable temperature vaporizer of a multidimensional gas chromatography system

A simple method involving direct introduction (DI) of cooked ham into a programmable temperature vaporizer and subsequent thermal desorption for multidimensional chromatographic analysis as a tool for studying changes of volatile compounds during food irradiation has been proposed. Analysis of non-irradiated samples showed four peaks in the precolumn, which were identified on the main column as peak 1, ethyl acetate; peak 2, a mixture of octanol and ethyl propanoate; peak 3, (R,R)-2,3-butanediol, and peak 4, nonanoic acid. (R,R) and (S,S)-2,3-butanediol were detected in samples irradiated at 8kGy, which may indicate that irradiation induces isomerisation. When a single cut was transferred from the precolumn to the main column, 1-tetradecene, n-pentadecane, 8-heptadecene and 1-hexadecene were detected in irradiated samples. This simple and easy method allows detection of radiolytic markers and isomerisation of 2,3-butanediol during irradiation of food.

Simultaneous enantioselective separation of polychlorinated biphenyls and their methyl sulfone metabolites by heart-cut MDGC: Determination of enantiomeric fractions in fish oils and cow liver samples

The potential of three capillary columns based on β-cyclodextrin (i.e., Chirasil-Dex, BGB-172, and BGB-176SE) has been studied for the simultaneous enantiomeric separation of polychlorinated biphenyls (PCBs) and methylsulfonyl metabolites of PCBs (MeSO(2)-PCBs) employing a heart-cut multidimensional gas chromatographic system (heart-cut MDGC). Among the columns studied, the BGB-176SE capillary column provided the best results, allowing the simultaneous enantioselective resolution of six MeSO(2)-PCBs and six chiral PCBs; the Chirasil-Dex column did not resolve any of the studied MeSO(2)-PCBs; and a poor resolution was obtained for three MeSO(2)-PCBs when the BGB-172 column was employed. The developed method was successfully applied to two fish oil and one cow liver samples commercially available, which showed different enantioselective pattern. PCBs 91 and 176 presented a clear enrichment of the second eluted atropisomer in codfish oil, whereas in fish oil sample, slight enrichment of the first eluted atropisomer of CB45 and the second eluted atropisomer of CB136 were observed.

Application of a multidimensional gas chromatography system with simultaneous mass spectrometric and flame ionization detection to the analysis of sandalwood oil

The production and trade of Indian sandalwood oil is strictly regulated, due to the impoverishment of the plantations; for such a reason, Australian sandalwood oil has been evaluated as a possible substitute of the Indian type. International directives report, for both the genuine essential oils, specific ranges for the sesquiterpene alcohols (santalols). In the present investigation, a multidimensional gas chromatographic system (MDGC), equipped with simultaneous flame ionization and mass spectrometric detection (FID/MS), has been successfully applied to the analysis of a series of sandalwood oils of different origin. A detailed description of the system utilized is reported. Three santalol isomers, (Z)-α-trans-bergamotol, (E,E)-farnesol, (Z)-nuciferol, epi-α-bisabolol and (Z)-lanceol have been quantified. LoD (MS) and LoQ (FID) values were determined for (E,E)-farnesol, used as representative of the oxygenated sesquiterpenic group, showing levels equal to 0.002% and 0.003%, respectively. A great advantage of the instrumental configuration herein discussed, is represented by the fact that identification and quantitation of target analytes are carried out in one step, without the need to perform two separate analyses.

Evaluation of tea tree oil quality and ascaridole: A deep study by means of chiral and multi heart-cuts multidimensional gas chromatography system coupled to mass spectrometry detection

The natural-like assessment of essential oils is a demanding task due to the growing trend toward adulterations. Usually chiral chromatography was used for this purpose due to the capability of assessing stereospecificity which is directly related to the enzymatic pathways of each plant species. On the other hand, the quality of an essential oil involves also the evaluation of its oxidative state, mainly connected with the age and storage conditions. In fact, some modifications in the chemical profile of the oil can occur if not properly preserved. Alterations of the components due to oxidative reactions lead to the formation of peroxides, endoperoxides and epoxides, such as ascaridole and 1,2,4-trihydroxymenthane, usually present in very low amount, formed by the oxidation of terpinen-4-ol and α-terpinene, respectively. Therefore, in the present research, the quality of Australian Tea Tree oil ( Melaleuca alternifolia (Maiden & Betche) Cheel, Myrtaceae) was investigated by means of a multi heart-cut multidimensional gas chromatographic system coupled to a mass spectrometer detector and by conventional enantio-GC. The MDGC system allowed the complete separation of the compounds of interest transferred from the first column to a second dimension based on a different separation mechanism. The MS detector at the end of the second column provided the identification of the peaks with high similarity values because of their high purities after the multidimensional separation. Method validation was carried out, in order to use this procedure for routine application, monitoring the repeatability of 1D retention times and 2D peak areas, LoD and LoQ. Finally, enantiomeric ratios for chiral compounds were established to support quality data obtained.

Racemization of S-(−)-nicotine during smoking and its relationship with pyrolysis process

The enantiomeric composition of nicotine in tobacco and cigarette smoke was analyzed by heart-cutting multidimensional gas chromatography (MDGC). The R-(+)-nicotine content of the total nicotine in cigarette smoke ranged from 2.6 to 3.6%, although essentially no R-(+)-nicotine was detected in tobacco. To investigate the formation mechanism of R-(+)-nicotine during the smoking process, S-(−)-nicotine reagent and tobacco were pyrolyzed by a micro-furnace pyrolyzer, and the chirality of nicotine in pyrolyzate was determined on-line by MDGC. The results showed that, no matter whether nicotine was pure or on tobacco, the racemization of S-(−)-nicotine was synchronous with pyrolytic decomposition. This work supports the hypothesis in the literature that the high temperatures involved in the smoking process are the main force for the racemization of nicotine. The MDGC system was composed of a pre-column of DB-1 (30 m × 0.25 mm i.d. × 0.25 μm film thickness) and a chiral column of DB-Cyclodex-B (60 m × 0.25 mm i.d. × 0.25 μm film thickness); FID and NPD were used as monitoring and analytical detectors.

Identification of three novel compounds in wine by means of a laboratory-constructed multidimensional gas chromatographic system

A laboratory-made off-line multidimensional GC–GC system has been optimized and applied to the isolation and identification of three novel aroma compounds in wine. The system comprises two independent chromatographs equipped with four-port manually actuated valves and fast capillary connectors that make it possible to quickly transfer a capillary trapping loop from the first to the second system. The first system includes a split/splitless injector, a thick phase semi-capillary column, the valve and both a flame ionization detection (FID) system and a sniffing port. The trapping loop lies outside the chromatograph and it is immersed in a Dewar with liquid nitrogen. The second system includes a programmable temperature vaporization (PTV) injector, the valve, the analytical column and two parallel detectors (a MS system and a sniffing port). The injection of large sample volumes (90 μl) in the first GC system and the general operation of the system have been optimized. The extract was obtained by purging the wine at 37 °C with a stream of nitrogen and trapping the volatiles in a bed containing 1 g LiChrolut EN. Fatty acids and alcohols were removed by washing the resins with a water/methanol solution containing 1% NaHCO 3, and volatiles were recovered with dichloromethane. The GC–MS analysis of the cuts obtained in the first GC system made it possible to identify by first time in wine the strong smelling compounds ethyl 2-, 3- and 4-methylpentanoate.

Fast enantiomeric analysis of a complex essential oil with an innovative multidimensional gas chromatographic system

The present research is focussed on the evaluation of a recently developed high performance multidimensional gas chromatographic (MDGC) system employed in the fast analysis of a series of chiral compounds contained in rosemary essential oil. The heart of the MDGC system consists in a simple transfer device for the rapid sequential re-injection of analyte “heart-cuts” from the first to the second dimension. The transfer system has no temperature restrictions, presents very low dead volumes and achieves multidimensional analysis through a pressure-balance mechanism. The MDGC set-up is characterized by two GC ovens (enabling independent temperature programming) and the possibility of mass spectrometric (MS) and/or flame ionization detection (FID). Multiple-cut conventional and fast MDGC–FID methods were developed and the results obtained compared, in order to evaluate the effectiveness of the system. In this respect, the rapid method provided the same analytical result in a greatly reduced time (approximately five times less). Furthermore, quali/quantitative data reproducibilty was very good. Fast MDGC was achieved by using micro-bore (0.1 mm I.D.) columns in both dimensions.

Two-dimensional gas chromatography analysis of components in fuel and fuel additives using a simplified heart-cutting GC system.

Multidimensional gas chromatography (MGC) using heart cutting is an old idea that can benefit from the performance of modern instruments and capillary columns to provide fast, reliable separation of target analytes from complex sample matrices. A simplified heart-cutting switch is described that uses these improvements to provide very narrow precise heart cuts between columns of different selectivity. This system is used to analyze ppm levels of 4,6-dimethydibenzothiophene in diesel fuel using a standard flame ionization detector instead of a complex sulfur-selective detector. MGC systems also offer the possibility of faster analysis speed by using two short columns of different selectivity instead of very long columns to resolve compounds from complex matrices. The analysis of alcohols in denatured fuel ethanol using the MGC system is performed over six times faster than the standard American Society for Testing and Materials methodology.

A portable multi‐dimensional gas chromatographic system for field applications

AbstractWe have constructed and tested a multi‐dimensional gas chromatographic system that can be utilized for field portable applications. The chromatographic system is capable of one‐dimensional separations and multi‐dimensional gas chromatographic (MDGC) separations in a single compact package. Three different general multi‐dimensional separation approaches are possible: column switching; traditional heart‐cutting; and comprehensive analyses. The MDGC system utilizes a simple 10‐port valving approach to accomplish these separations to a single point detector. Because of this valving scheme no hardware change is required to switch between the heart‐cut and the comprehensive separation modes, only a software methodology change is required. An additional advantage of this valving approach is that 100% of the first‐dimensional effluent is sampled to the second dimension for separation. The system is capable of rapid column heating (room temperature to 250°C in approximately 10 s) and rapid column cooling (250°C to room temperature within approximately 30 s). Preliminary results for heart‐cut and comprehensive separations that target five compounds against high concentration levels of complex background are illustrated.

Bioanalysis of the enantiomers of (+/-)-sarin using automated thermal cold-trap injection combined with two-dimensional gas chromatography.

A fully automated multidimensional gas chromatographic system with thermal desorption injection and alkali flame detection was developed for analysis of the enantiomers of the nerve agent (+/-)-sarin. The chiral stationary phase was CP Cyclodex B on which the sarin enantiomers were completely resolved. The absolute detection limit was 2.5 pg per enantiomer. The method is intended to be used for the analysis of the sarin enantiomers in biological samples. For this purpose, sarin was isolated from guinea pig blood via solid-phase extraction. Deuterated sarin was used as internal standard. Stabilization of sarin in the blood sample by acidification and addition of an excess of a competitive organophosphorus compound (neopentyl sarin) appeared to be essential. The absolute recovery of the extraction procedure was 60%, whereas the recovery relative to the internal standard was 100%.

Evaluation of a Semi-Automated Multidimensional Gas Chromatography-Infrared-Mass Spectrometry System for Irritant Analysis

The use of a semi-automated, multidimensional gas chromatography (MDGC) Fourier transform infrared (FT-IR) mass spectrometry (MS) system in the determination of components causing contact dermatitis has been investigated. Fragrances are widely used in cosmetic and household products and are the leading cause of contact dermatitis. Such products contain numerous components such as emulsifiers, thickeners, solubilizers, pigments, antioxidants, and many other compounds, which can make it difficult to isolate the compound of interest. MDGC has the capability for component analysis in such complex matrices. A semi-automated MDGC system, which consists of a commercial instrument modified in our laboratory to include two computer controlled valves and a single trap which is manually controlled was evaluated for analysis of irritants in a total of thirteen soaps. Using heartcutting techniques, components causing dermatitis were identified in eight of the thirteen soaps by examining both the infrared and mass spectra obtained and matching them with computer spectral libraries. Results from these analyses show that a baby soap and three other mild soaps were free of irritants. Irritants were identified in the remaining eight soaps. In addition, to demonstrate the versatility of the semi-automated system, the enantiomeric composition of a chiral irritant in two soaps also was determined.

Quantitative aspects of a valve-based, multi-stage multidimensional gas chromatography-infrared spectroscopy-mass spectrometry system

Use of high-resolution capillary gas chromatography coupled with infrared and mass spectral detectors is a very powerful qualitative analytical technique. However, accurate qualitative analyses with spectroscopic detection requires that the separation system provide the detectors with pure components. Unfortunately, in very complex mixtures, this is virtually impossible when single-stage separations are employed. This paper describes the sample recycling capabilities of a valve-based multidimensional gas chromatography system equipped with both infrared and mass spectral detectors. Sample recycle efficiencies, valve adsorption effects and cycle-to-cycle reproducibility are considered. Mixtures including the Grob test mixture were analyzed and it was found that 35 out of the 40 total components examined could be recycled six times or more following injection of 500 ng or less of each component. Additionally, the first demonstration of a 23-stage recycling experiment with several components of a chlorinated hydrocarbon mixture is shown. This demonstrates the plausibility of performing GC n experiments, where n is the number of separation stages, with values of n up to 23 for these components. It is also shown that mechanical valves generally do not have deleterious effects on the majority of these components. The main limitations of the system appear to be the design of the heating system and the manual control of the pressure and flow switching systems. The applicability of the present results to qualitative analyses are discussed.

Construction of an all‐glass/fused silica, zero dead volume multidimensional gas chromatographic system using press‐fit connectors: Preliminary results

AbstractA multidimensional gas chromatographic system has been constructed using commercially available press‐fit connectors, glass splitters, and fused silica lines. In this new design all the lines are continuously purged with carrier gas, ensuring no dead volumes in the chromatographic path. Some preliminary results and practical considerations are presented.

Multidimensional gas chromatography with parallel cryogenic traps

In its most common form, multidimensional gas chromatography (MDGC) has been restricted to used of a single intermediate cryogenic trap between two serially coupled columns. This paper describes successful implementation of a multi-port valve MDGC system with two parallel cryogenic traps interposed between a first stage GC precolumn and a second stage GC analytical column. Using this strategy, it is possible to accomodate the constraints of infrared and mass spectrometry detectors in a directly linked structure elucidation system

Some applications of multidimensional gas chromatography to the enrichment of minor components in essential oil analysis

AbstractThe use of multidimensional gas chromatography (MDGC) for the analysis of essential oils is gaining in importance. A rarely used application consists in the enrichment of minor components through a MDGC system provided with a cold trap between trap column and analytical column. Under suitable conditions, in fact, the cold‐trap can store a trapped compound (or a fraction) for a long time. Consequently, the same fraction can be heart‐cut from several successive chromatographic runs on the first column and stored together in order to accumulate trace compounds; afterwards the accumulated fraction can be injected in the analytical column. The possibilities of this technique will illustrated through some examples of analysis of complex essential oils.